Novel 4,5-disubstituted 1,3-thiazol-2-yloxyacetamide herbicides

ABSTRACT

Herbicidally active novel 4,5-disubstituted 1,3-thiazol-2-yloxyacetamides of the formula ##STR1## in which R 1  is fluorine or chlorine, 
     R 2  is alkyl or halogenoalkyl, and 
     R 3  and R 4  each independently is alkyl, alkenyl, alkinyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, halogenoalkyl, alkoxyalkyl, alkoxyalkyleneoxy, alkoxy, aralkyl or optionally substituted aryl, or 
     R 3  and R 4 , conjointly with the nitrogen atom to which they are bonded form an optionally substituted, heterocyclic ring which can contain further hetero-atoms.

This is a division of application Ser. No. 826,479, filed Feb. 5, 1986,now Pat. No. 4,788,291.

The invention relates to a new 4,5-disubstituted1,3-thiazol-2-yloxyacetamides, a process for their preparation and theiruse as herbicides.

It is already known that certain 4,5-disubstituted1,3-thiazol-2-yloxyacetamides, such as, for example,2-(4,5-dichloro-1,3-thiazol-2-yloxy)-N,N-diethylacetamide, possessherbicidal, in particular also selectively herbicidal, properties(compare, for example, EP-OS (European Laid-Open Specification) 18,497).

However, the herbicidal activity of these previously known compoundstoward weeds, as well as their selectively toward improvement cropplants, is not always fully satisfactory in all use sectors.

There have been found new 4,5-disubstituted1,3-thiazol-2-yloxyacetamides of the general formula (I) ##STR2## inwhich R¹ represents fluorine or chlorine,

R² represents alkyl or halogenoalkyl and

R³ and R⁴ independently of one another represent alkyl, alkenyl,alkinyl, optionally substituted cycloalkyl or optionally substitutedcycloalkenyl, halogenoalkyl, alkoxyalkyl, alkoxyalkyleneoxy or alkoxy,aralkyl or optionally substituted aryl or conjointly with the nitrogenatom to which they are bonded represent an optionally substituted,saturated or unsaturated, heterocyclic ring which can contain furtherhetero-atoms.

Further, it has been found that the new 4,5-disubstituted1,3-thiazol-2-yloxyacetamides of the general formula (I) are obtainedwhen 4,5-disubstituted 1,3-thiazoles of the formula (II) ##STR3## inwhich R¹ and R² have the abovementioned meaning and

A represents an electron-attracting leaving group,

are reacted with glycolic acid amides of the formula (III) ##STR4## inwhich R³ and R⁴ have the abovementioned meaning,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor as well as, if appropriate, in the presenceof a catalyst.

Finally, it has been found that the new 4,5-disubstituted1,3-thiazol-2-yloxyacetamides of the formula (I) possess herbicidal, inparticular also selectively herbicidal, properties.

Surprisingly, the 4,5-disubstituted 1,3-thiazol-2-yloxyacetamidesaccording to the invention, of the formula (I), exhibit substantiallyimproved herbicidal activity against common weeds which are difficult tocombat, and relatively good toleration by important crop plants, incomparison with the 4,5-disubstituted 1,3-thiazol-2-yloxyacetamidespreviously known from the state of the art, such as, for example,2-(4,5-dichloro-1,3-thiazol-2-yloxy)-N,N-diethylacetamide which are,chemically and in respect of their action, closely related compounds.

The formula (I) provides a general definition of the 4,5-disubstituted1,3-thiazol-2-yloxyacetamides according to the invention. Preferredcompounds of the formulat (II) are those in which

R¹ represents fluorine or chlorine,

R² represents straight-chain or branched alkyl or halogenoalkyl eachwith 1 to 4 carbon atoms and, where appropriate, 1 to 9 identical ordifferent halogen atoms, such as, in particular, fluorine, chlorine orbromine and

R³ and R⁴ independently of one another represent straight-chain orbranched alkyl with 1 to 8 carbon atoms, straight-chain or branchedalkenyl and alkinyl each with 2 to 8 carbon atoms, cycloalkyl orcycloalkenyl, each with 3 to 7 carbon atoms, which optionally have oneor more identical or different substituents (suitable substituentsbeing, in particular, alkyl radicals with 1 to 4 carbon atoms),straight-chain or branched alkoxy, alkoxyalkyleneoxy or alkoxyalkyl eachwith 1 to 8 carbon atoms in the individual alkyl or alkylene moieties,halogenoalkyl with 1 to 8 carbon atoms and 1 to 5 halogen atoms,especially fluorine, chlorine and bromine, aralkyl with 6 to 10 carbonatoms in the aryl moiety and 1 to 2 carbon atoms in the alkyl moiety, aswell as aryl with 6 to 10 carbon atoms which optionally has one or moreidentical or different substituents (possible substituents beinghalogen, straight-chain or branched alkyl, alkoxy or alkylthio each with1 to 4 carbon atoms, and halogenoalkyl, halogenoalkoxy andhalogenoalkylthio each with 1 to 2 carbon atoms and 1 to 5 halogenatoms, especially fluorine, chlorine and bromine, as well as nitro), or

R³ and R⁴ together with the nitrogen atom to which they are bondedrepresent a saturated or unsaturated, 5- to 7-membered heterocyclic ringwhich optionally has one or more identical or different substituents,possible substituents being straight-chain or branched alkyl with 1 to 6carbon atoms, also in the form of a fused ring system, aryl with 6 to 10carbon atoms, also in the form of a fused ring system, or dioxyalkylenewith 2 to 3 arbon atoms.

Particularly preferred compounds of the formula (I) are those in which

R¹ represents fluorine or chlorine,

R² represents methyl, trifluoromethyl, difluoromethyl, fluoromethyl,trichloromethyl, dichloromethyl, chloromethyl, fluorodichloromethyl ordifluorochloromethyl and

R³ and R⁴ independently of one another represent straight-chain orbranched alkyl with 1 to 6 carbon atoms, straight-chain or branchedalkenyl and alkinyl each with 2 to 6 carbon atoms, cycloalkyl orcycyloalkenyl with 5 to 7 carbon atoms which are optionally mono- totri-substituted by methyl or ethyl, the substituents being identical ordifferent, alkoxy, alkoxyalkyleneoxy or alkoxyalkyl, each of which isstraight-chain or branched and has 1 to 6 carbon atoms in the individualalkyl moieties, halogenoalkyl with 1 to 6 carbon atoms and 1 to 5halogen atoms, especially fluorine, bromine and chlorine, benzyl as wellas phenyl which optionally has one to three identical or differentsubstituents, particularly preferred substituents being methyl, ethyl,methoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, fluorine, chlorine or nitro; or

R³ and R⁴ together with the nitrogen atom to which they are bondedrepresent a heterocyclic ring of the formula ##STR5## which optionallyhas one to three identical or different substituents, particularlypreferred substituents being methyl, ethyl and phenyl.

Specifically, the following compounds of the general formula (I) may bementioned in addition to the compounds mentioned in the preparationexamples:

                                      TABLE I                                     __________________________________________________________________________     ##STR6##                                                                      R.sup.1                                                                         R.sup.2                                                                           R.sup.3   R.sup.4 OR                                                                                 ##STR7##                                        __________________________________________________________________________    Cl                                                                              CF.sub.3                                                                          CH.sub.3  CH.sub.3 OCH.sub.2                                            Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR8##                                                     Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR9##                                                     Cl                                                                              CF.sub.3                                                                          CH.sub.3  F.sub.3 CCH.sub.2                                             Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR10##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR11##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR12##                                                    Cl                                                                              CF.sub.3                                                                          C.sub.2 H.sub.5                                                                         CH.sub.2CHCH.sub.2                                            Cl                                                                              CF.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                            Cl                                                                              CF.sub.3                                                                                                  ##STR13##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR14##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR15##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR16##                                       Cl                                                                              CF.sub.3                                                                          CH.sub.3  HCCCH.sub.2                                                   Cl                                                                              CF.sub.3                                                                          CH.sub.3 O                                                                               ##STR17##                                                    Cl                                                                              CF.sub.3                                                                          (CH.sub.3).sub.2 CHO                                                                    C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2O                           Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR18##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR19##                                                    Cl                                                                              CF.sub.3                                                                          (CH.sub.3).sub.2 CH                                                                     (CH.sub.3).sub.2 CHO                                          Cl                                                                              CF.sub.3                                                                           ##STR20##                                                                              CH.sub.3 OCH.sub.2                                            Cl                                                                              CF.sub.3                                                                          CH.sub.3 (CH.sub.2).sub.3                                                               CH.sub.3(CH.sub.2).sub.3                                      Cl                                                                              CF.sub.3                                                                          C.sub.2 H.sub.5                                                                         (CH.sub.3).sub.2 CH                                           Cl                                                                              CF.sub.3                                                                          (CH.sub.3).sub.2 CH                                                                     C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 O                          Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR21##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR22##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR23##                                                    Cl                                                                              CF.sub.3                                                                                                  ##STR24##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR25##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR26##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR27##                                       Cl                                                                              CF.sub.3                                                                          CH.sub.3  CH.sub.2CHCH.sub.2                                            Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR28##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR29##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3  CH.sub.3 (CH.sub.2).sub.3                                     Cl                                                                              CF.sub.3                                                                          CH.sub.3                                                                                 ##STR30##                                                    Cl                                                                              CF.sub.3                                                                          CH.sub.3  CH.sub.2CH                                                    Cl                                                                              CF.sub.3                                                                          C.sub.2 H.sub.5                                                                         CH.sub.2CH                                                    Cl                                                                              CF.sub.3                                                                                                  ##STR31##                                       Cl                                                                              CF.sub.3                                                                                                  ##STR32##                                       F CF.sub.3                                                                          CH.sub.3  CH.sub.3 OCH.sub.2                                            F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR33##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR34##                                                    F CF.sub.3                                                                          CH.sub.3  F.sub.3 CCH.sub.2                                             F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR35##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR36##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR37##                                                    F CF.sub.3                                                                          C.sub.2 H.sub.5                                                                         CH.sub.2CHCH.sub.2                                            F CF.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                            F CF.sub.3                   . -                                                                            ##STR38##                                       F CF.sub.3                                                                                                  ##STR39##                                       F CF.sub.3                                                                                                  ##STR40##                                       F CF.sub.3                                                                                                  ##STR41##                                       F CF.sub.3                                                                          CH.sub.3  HCCCH.sub.2                                                   F CF.sub.3                                                                          CH.sub.3 O                                                                               ##STR42##                                                    F CF.sub.3                                                                          (CH.sub.3).sub.2 CHO                                                                    C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2O                           F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR43##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR44##                                                    F CF.sub.3                                                                          (CH.sub.3).sub.2 CH                                                                     (CH.sub.3).sub.2 CHO                                          F CF.sub.3                                                                           ##STR45##                                                                              CH.sub.3 OCH.sub.2                                            F CF.sub.3                                                                          CH.sub.3 (CH.sub.2).sub.3                                                               CH.sub.3(CH.sub.2).sub.3                                      F CF.sub.3                                                                          C.sub.2 H.sub.5                                                                         (CH.sub.3).sub.2 CH                                           F CF.sub.3                                                                          (CH.sub.3).sub.2 CH                                                                     C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 O                          F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR46##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR47##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR48##                                                    F CF.sub.3                                                                                                  ##STR49##                                       F CF.sub.3                                                                                                  ##STR50##                                       F CF.sub.3                                                                                                  ##STR51##                                       F CF.sub.3                                                                                                  ##STR52##                                       F CF.sub.3                                                                          CH.sub.3  CH.sub.2CHCH.sub.2                                            F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR53##                                                    F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR54##                                                    F CF.sub.3                                                                          CH.sub.3  CH.sub.3 (CH.sub.2).sub.3                                     F CF.sub.3                                                                          CH.sub.3                                                                                 ##STR55##                                                    F CF.sub.3                                                                          CH.sub.3  CH.sub.2CH                                                    F CF.sub.3                                                                          C.sub.2 H.sub.5                                                                         CH.sub.2CH                                                    F CF.sub.3                                                                                                  ##STR56##                                       F CF.sub.3                                                                                                  ##STR57##                                       F CHF.sub.2                                                                         CH.sub.3  CH.sub.3 OCH.sub.2                                            F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR58##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR59##                                                    F CHF.sub.2                                                                         CH.sub.3  F.sub.3 CCH.sub.2                                             F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR60##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR61##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR62##                                                    F CHF.sub.2                                                                         C.sub.2 H.sub.5                                                                         CH.sub.2CHCH.sub.2                                            F CHF.sub.2                                                                         CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                            F CHF.sub.2                                                                                                 ##STR63##                                       F CHF.sub.2                                                                                                 ##STR64##                                       F CHF.sub.2                                                                                                 ##STR65##                                       F CHF.sub.2                                                                                                 ##STR66##                                       F CHF.sub.2                                                                         CH.sub.3  HCCCH.sub.2                                                   F CHF.sub.2                                                                         CH.sub.3 O                                                                               ##STR67##                                                    F CHF.sub.2                                                                         (CH.sub.3).sub.2 CHO                                                                    C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2O                           F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR68##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR69##                                                    F CHF.sub.2                                                                         (CH.sub.3).sub.2 CH                                                                     (CH.sub.3).sub.2 CHO                                          F CHF.sub.2                                                                          ##STR70##                                                                              CH.sub.3 OCH.sub.2                                            F CHF.sub.2                                                                         CH.sub.3 (CH.sub.2).sub.3                                                               CH.sub.3(CH.sub.2).sub.3                                      F CHF.sub.2                                                                         C.sub.2 H.sub.5                                                                         (CH.sub.3).sub.2 CH                                           F CHF.sub.2                                                                         (CH.sub.3).sub.2 CH                                                                     C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 O                          F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR71##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR72##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR73##                                                    F CHF.sub.2                                                                                                 ##STR74##                                       F CHF.sub.2                                                                                                 ##STR75##                                       F CHF.sub.2                                                                                                 ##STR76##                                       F CHF.sub.2                                                                                                 ##STR77##                                       F CHF.sub.2                                                                         CH.sub.3  CH.sub.2CHCH.sub.2                                            F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR78##                                                    F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR79##                                                    F CHF.sub.2                                                                         CH.sub.3  CH.sub.3 (CH.sub.2).sub.3                                     F CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR80##                                                    F CHF.sub.2                                                                         CH.sub.3  CH.sub.2CH                                                    F CHF.sub.2                                                                         C.sub.2 H.sub.5                                                                         CH.sub.2CH                                                    F CHF.sub.2                                                                                                 ##STR81##                                       F CHF.sub.2                                                                                                 ##STR82##                                       F CH.sub.2 F                                                                        CH.sub.3  CH.sub.3 OCH.sub.2                                            F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR83##                                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR84##                                                    F CH.sub.2 F                                                                        CH.sub.3  F.sub.3 CCH.sub.2                                             F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR85##                                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR86##                                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR87##                                                    F CH.sub.2 F                                                                        C.sub.2 H.sub.5                                                                         CH.sub.2CHCH.sub.2                                            F CH.sub.2 F                                                                        CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                            F CH.sub.2 F                                                                                                ##STR88##                                       F CH.sub.2 F                                                                                                ##STR89##                                       F CH.sub.2 F                                                                                                ##STR90##                                       F CH.sub.2 F                                                                                                ##STR91##                                       F CH.sub.2 F                                                                        CH.sub.3  HCCCH.sub.2                                                   F CH.sub.2 F                                                                        CH.sub.3 O                                                                               ##STR92##                                                    F CH.sub.2 F                                                                        (CH.sub.3).sub.2 CHO                                                                    C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2O                           F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR93##                                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR94##                                                    F CH.sub.2 F                                                                        (CH.sub.3).sub.2 CH                                                                     (CH.sub.3).sub.2 CHO                                          F CH.sub.2 F                                                                         ##STR95##                                                                              CH.sub.3 OCH.sub.2                                            F CH.sub.2 F                                                                        CH.sub.3 (CH.sub.2).sub.3                                                               CH.sub.3(CH.sub.2).sub.3                                      F CH.sub.2 F                                                                        C.sub.2 H.sub.5                                                                         (CH.sub.3).sub.2 CH                                           F CH.sub. 2 F                                                                       (CH.sub.3).sub.2 CH                                                                     C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 O                          F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR96##                                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR97##                                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR98##                                                    F CH.sub.2 F                                                                                                ##STR99##                                       F CH.sub.2 F                                                                                                ##STR100##                                      F CH.sub.2 F                                                                                                ##STR101##                                      F CH.sub.2 F                                                                                                ##STR102##                                      F CH.sub.2 F                                                                        CH.sub.3  CH.sub.2CHCH.sub.2                                            F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR103##                                                   F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR104##                                                   F CH.sub.2 F                                                                        CH.sub.3  CH.sub. 3 (CH.sub.2).sub.3                                    F CH.sub.2 F                                                                        CH.sub.3                                                                                 ##STR105##                                                   F CH.sub.2 F                                                                        CH.sub.3  CH.sub.2CH                                                    F CH.sub.2 F                                                                        C.sub.2 H.sub.5                                                                         CH.sub.2CH                                                    F CH.sub.2 F                                                                                                ##STR106##                                      F CH.sub.2 F                                                                                                ##STR107##                                      Cl                                                                              CHF.sub.2                                                                         CH.sub.3  CH.sub.3 OCH.sub.2                                            Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR108##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR109##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3  F.sub.3 CCH.sub.2                                             Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR110##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR111##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR112##                                                   Cl                                                                              CHF.sub.2                                                                         C.sub.2 H.sub.5                                                                         CH.sub.2CHCH.sub.2                                            Cl                                                                              CHF.sub.2                                                                         CH.sub.2CHCH.sub.2                                                                      CH.sub.2CHCH.sub.2                                            Cl                                                                              CHF.sub.2                                                                                                 ##STR113##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR114##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR115##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR116##                                      Cl                                                                              CHF.sub.2                                                                         CH.sub.3  HCCCH.sub.2                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3 O                                                                               ##STR117##                                                   Cl                                                                              CHF.sub.2                                                                         (CH.sub.3).sub.2 CHO                                                                    C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2O                           Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR118##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR119##                                                   Cl                                                                              CHF.sub.2                                                                         (CH.sub.3).sub.2 CH                                                                     (CH.sub.3).sub.2 CHO                                          Cl                                                                              CHF.sub.2                                                                          ##STR120##                                                                             CH.sub.3 OCH.sub.2                                            Cl                                                                              CHF.sub.2                                                                         CH.sub.3 (CH.sub.2).sub.3                                                               CH.sub.3(CH.sub.2).sub.3                                      Cl                                                                              CHF.sub.2                                                                         C.sub.2 H.sub.5                                                                         (CH.sub.3).sub.2 CH                                           Cl                                                                              CHF.sub.2                                                                         (CH.sub.3).sub.2 CH                                                                     C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 O                          Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR121##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR122##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR123##                                                   Cl                                                                              CHF.sub.2                                                                                                 ##STR124##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR125##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR126##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR127##                                      Cl                                                                              CHF.sub.2                                                                         CH.sub.3  CH.sub.2CHCH.sub.2                                            Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR128##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR129##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3  CH.sub.3 (CH.sub.2).sub.3                                     Cl                                                                              CHF.sub.2                                                                         CH.sub.3                                                                                 ##STR130##                                                   Cl                                                                              CHF.sub.2                                                                         CH.sub.3  CH.sub.2CH                                                    Cl                                                                              CHF.sub.2                                                                         C.sub.2 H.sub.5                                                                         CH.sub.2CH                                                    Cl                                                                              CHF.sub.2                                                                                                 ##STR131##                                      Cl                                                                              CHF.sub.2                                                                                                 ##STR132##                                      __________________________________________________________________________

If, for example, 2-chloro-4-fluoro-5-trifluoromethyl-1,3-thiazole andglycolic acid N-methylanilide are used as starting materials, the courseof the reaction of the process according to the invention can berepresented by the following equation: ##STR133##

The formula (II) provides a general definition of the 4,5-disubstituted1,3-thiazoles required as starting materials for carrying out theprocess according to the invention. Preferred compounds of the formula(II) are those in which R¹ and R² represent those radicals which havealready been mentioned, in connection with the description of thecompounds according to the invention, of the formula (I), as beingpreferred for these substituents; A preferably represents halogen,especially chlorine or fluorine.

The 4,5-disubstituted 1,3-thiazoles of the formula (II) were notpreviously known (an exception is2,4-dichloro-5-trifluoromethyl-1,3-thiazole, compare J. Heterocycl.Chem. 13, 1297-1304 (1976), which had not however previously beenisolated).

4,5-Disubstituted 1,3-thiazoles of the formula (IIa) ##STR134## whichwere not previously known and in which A', R^(1') and R^(2') have thesame meaning as the above-mentioned substituents A, R¹ and R², but A'and R^(1') do not simultaneously represent chlorine if R^(2') representstrifluoromethyl,

are obtained when thiazolidine-diones of the formula (IV) ##STR135## inwhich R^(2") represents alkyl, especially methyl,

are reacted with phosphorus oxychloride, if appropriate in the presenceof a catalyst, such as, for example, N,N-dimethylformamide, atteperatures between +50° C. and +120° C. and, where appropriate, in a2nd stage the 2,4-dichloro-1,3-thiazoles thus obtained, of the formula(IIb) ##STR136## in which R^(2") has the abovementioned meaning,

are reacted with chlorine, if appropriate in the presence of a diluent,such as, for example, carbon tetrachloride or phosphorus oxychloride, attemperatures between 50° C. and 250° C. and, if appropriate, in a 3rdstage the 5-chloroalkyl-2,4-dichloro-1,3-thiazoles thus obtainable, ofthe formula (IIc) ##STR137## in which R^(2'") represents chloroalkyl,especially chloromethyl, dichloromethyl or trichloromethyl,

are fluorinated with hydrofluoric acid or an alkali metal fluoride suchas, for example, potassium fluoride, if appropriate in the presence of adiluent, such as, for example, tetramethylenesulphone, if appropriateunder pressure, at temperatures between +40° C. and +200° C.

The thiazolidine-diones of the formula (IV) are known (compare, forexample, J. prakt. Chemie (2) 123, 114-121 (1931)) or can be prepared inanalogy to known processes.

The formula (III) provides a general definition of the glycolic acidamides furthermore required as starting materials for carrying out theprocess according to the invention. In this formula (III), R³ and R⁴preferably represent those radicals which have already been mentioned asbeing preferred for these substituents in the description of thecompounds according to the invention, of the formula (I). The glycolicacid amides of the formula (III) are also known (compare, for example,DE-OS (German Published Specification) 2,904,490, EP-OS (EuropeanPublished Specification) 5,501, EP-OS (European Published Specification)29,171, DE-OS (German Published Specification) 3,038,598 and DE-OS(German Published Specication) 3,244,956).

Possible diluents for the process according to the invention are organicor inorganic solvents. Preferred diluents are hydrocarbons, such astoluene or cyclohexane, halogenohydrocarbons, such as methylenechloride, chloroform, dichloroethane or chlorobenzene, ketones, such asacetone or methyl isobutyl ketone, ethers, such as diethyl ether,diisopropyl ether or methyl t-butyl ether, alcohols, such as methanol,ethanol or isopropanol, amides, such as dimethylformamide ordimethylacetamide, sulphoxides, such as dimethylsulphoxide, water oraqueous salt solutions.

The salts used are preferably chlorides or sulphates of alkali metals oralkaline earth metals, such as, for example, sodium chloride, potassiumchloride or calcium chloride. Sodium chloride is particularly preferred.

The process according to the invention is advantageously carried outusing acid acceptors. As such, strongly basic alkali metal and alkalineearth metal compounds, for example oxides, such as, for example, sodium,potassium, magnesium and calcium oxide, hydroxides, such as, forexample, sodium, potassium, magnesium and calcium hydroxide and/orcarbonate, such as, for example, sodium, potassium, magnesium andcalcium carbonate, are preferably used.

The addition of 0.01 to 10% by weight (based on glycolic acid amideemployed, of the formula (III)) of a phase transfer catalyst may provideadvantageous in some cases. As examples of such catalysts there may bementioned:

Tetrabutylammonium chloride, tetrabutylammonium bromide,tributyl-methylphosphonium bromide, trimethyl-C₁₃ /C₁₅ -alkyl-ammoniumchloride, dibenzyl-dimethylammonium methylsulphate, dimethyl-C₁₂ /C₁₄-alkyl-benzylammonium chloride, tetrabutylammonium hydroxide,18-crown-6, triethylbenzylammonium chloride, trimethylbenzylammoniumchloride and tetraethylammonium bromide.

In the process according to the invention, the reaction temperatures canbe varied within a substantial range. They are in general between -50°C. and +100° C., preferably between -20° C. and +100° C.

The process according to the invention is in general carried out undernormal pressure but can also be carried out under elevated or reducedpressure, approximately between 0.1 and 10 bar.

To carry out the process according to the invention, in general 0.1 to10 moles, preferably 0.8 to 1.2 moles, of glycolic acid amide of theformula (III) and 0.5 to 10 moles, preferably 0.5 to 3 moles, of baseare employed per mole of 4,5-disubstituted 1,3-thiazole of the formula(II). The sequence of addition of the reactants can be varied asdesired, and it is also possible to introduce all componentssimultaneously into the reaction vessel. The reaction can be carried outcontinuously or discontinuously. Working up is carried out in the usualmanner.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,in particular, weed-killers. By weeds in the broadest sense there are tobe understood all plants which grow in locations where they areundersired. Whether the compounds according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochloria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings, and hopfields, andfor the selective combating of weeds in annual cultures.

In addition to an excellent action against weeds, the active compoundsaccording to the invention also show good toleration by important cropplants and can therefore be employed as selective agents for combatingweeds in dicotyledon crops, such as soy beans, cotton, sugar beet andothers.

In addition, the active compounds according to the invention, when usedin appropriate amounts, also exhibit a powerful fungicidal andplant-growth regulating action.

The active compounds according to the invention can be employed withparticularly good success for combating diseases of rice, such as, forexample, the pathogen of rice blast disease (Pyricularia oryzae).

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances and incoating compositions for use on seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans, fumigatingcoils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can for example also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable for example ground naturalminerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, and ground synthetic mineralssuch as highly dispersed silicic acid, alumina and silicates; as solidcarriers for granules there are suitable for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable for example non-ionic and anionic emulsifiers, suchas polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcoholethers, for example alkylaryl polyglycol ethers, alkyl sulphonates,alkyl sulphates, aryl sulphonates, as well as albumin hydrolysisproducts; as dispersing agents there are suitable for examplelignin-sulphite waste liquors and methylcellulose.

Adhesives, such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices can be used in theformulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetatesas well as natural phospholipids, such as cephalins and lecithins, andsynthetic phospholipids. Further possible additives include mineral oilsand vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin, azo and metal phthalocyanine dyestuffs, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90% by weight.

When used as herbicides, the active compounds according to theinvention, as such or in the form of their formulations, can also beused, for combating weeds, as mixtures with known herbicides, finishedformulations or tank mixing being possible.

In the mixtures it is possible to use known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dioneor N-(2-benzothiazol)-N,N'-dimethyl-urea for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one for combating weeds insugar beet and4-amino-6-(1,2-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one forcombating weeds in soy beans. Mixtures withN,N-dimethyl-N'-(trifluoromethylphenyl)-urea, chloroacetic acidN-(methoxymethyl)-2,6-diethylanilide,2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide;2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline;5-amino-4-chloro-2-phenyl-2,3-dihydro-3-oxo-pyridazine;N,N-diisopropyl-S-(2,3,3-trichloroallyl)-thiolcarbamate;2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-methanesulphonate;1-isobutylaminocarbonyl-2-imidazolidinone;N-cyclohexyl-N,S-diethyl-thiolcarbamate;3-cyclohexyl-5,6-trimethyleneuracil, with other heteroaryloxyacetamidesor aryl- or heteroaryloxy-phenoxy-propionic acids can also be used. Somemixtures surprisingly also show a synergistic action.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure are also possible.

The active compounds can be used as such, as their formulations or asthe use forms prepared therefrom by further dilution, such asready-to-use solutions, suspensions, emulsions, powders, pastes andgranules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied bothbefore and after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used for application as herbicides are between 0.01 and 10kg of active compound per hectare of soil surface, preferably between0.05 and 5 kg per hectare.

The examples which follow serve further to explain the invention.

PREPARATION EXAMPLES EXAMPLE 1 ##STR138##

8.5 g (0.05 mol) of 2-chloro-4-fluoro-5-difluoromethyl-1,3-thiazole in10 ml of acetonitrile are slowly added dropwise, with stirring, to 7.9 g(0.05 mol) of hydroxyacetic acid N,N-hexamethylenimide and 3.1 g (0.05mol) of potassium hydroxide in 100 ml of isopropanol at -20° C. andafter completion of the addition the mixture is stirred for a further 12hours at -20° C. When the starting product is no longer detectable inthe thin-layer chromatogram, the reaction mixture is poured into waterand the crystalline product is filtered off and rinsed with water and asmall amount of cold ligroin. 12 g (80% of theory) of2-(4-fluoro-5-difluoromethylthiazol-2-yloxy)acetic acidN,N-hexamethylenimide of melting point 66° C. are obtained.

Processing analogously, and in accordance with the general preparationstatements, the following compounds of the general formula (I)--compareTable 2--are obtained: ##STR139## (if the substances are obtained asoils, they are isolated, in the generally customary manner, byextraction from the aqueous mixture, using an organic solvent).

                                      TABLE 2                                     __________________________________________________________________________     Example No.                                                                          R.sup.1                                                                         R.sup.2                                                                           ##STR140##      Physical data                                   __________________________________________________________________________    2      Cl                                                                              CH.sub.3                                                                           ##STR141##     M.p.: 61° C.                              3      Cl                                                                              CH.sub.3                                                                           ##STR142##     M.p.: 42° C.                              4      Cl                                                                              CH.sub.3                                                                           ##STR143##     M.p.: 82° C.                              5      Cl                                                                              CHCl.sub.2                                                                         ##STR144##     M.p.: 94° C.                              6      Cl                                                                              CF.sub.2 Cl                                                                        ##STR145##     M.p.: 84° C.                              7      Cl                                                                              CF.sub.2 Cl                                                                        ##STR146##     n.sub.D.sup.20 = 1.5060                          8      Cl                                                                              CF.sub.2 Cl                                                                        ##STR147##     n.sub. D.sup.20 = 1.4950                         9      Cl                                                                              CHF.sub.2                                                                          ##STR148##     n.sub.D.sup.20 = 1.4891                          10     Cl                                                                              CHF.sub.2                                                                          ##STR149##     M.p.: 64° C.                              11     Cl                                                                              CHF.sub.2                                                                          ##STR150##     M.p.: 72° C.                              12     F CHF.sub.2                                                                          ##STR151##     M.p.: 78° C.                              13     F CHF.sub.2                                                                          ##STR152##     M.p.: 50° C.                              14     Cl                                                                              CHF.sub.2                                                                          ##STR153##     M.p.: 74° C.                              15     Cl                                                                              CF.sub.3                                                                           ##STR154##     M.p.: 115° C.                             16     Cl                                                                              CF.sub.3                                                                           ##STR155##     M.p.: 70° C.                              17     Cl                                                                              CF.sub.3                                                                           ##STR156##     M.p.: 39° C.                              18     Cl                                                                              CF.sub.3                                                                           ##STR157##     M.p.: 66° C.                              19     Cl                                                                              CF.sub.3                                                                           ##STR158##     M.p.: 58° C.                              20     Cl                                                                              CF.sub.3                                                                           ##STR159##     M.p.: 72° C.                              21     Cl                                                                              CF.sub.3                                                                           ##STR160##     n.sub.D.sup.20 = 1.4908                          22     Cl                                                                              CF.sub.3                                                                           ##STR161##     n.sub.D.sup.20 = 1.4965                          23     Cl                                                                              CF.sub.3                                                                           ##STR162##     n.sub.D.sup.20 = 1.4774                          24     Cl                                                                              CF.sub.3                                                                           ##STR163##     n.sub.D.sup.20 = 1.4715                          25     Cl                                                                              CF.sub.3                                                                           ##STR164##     n.sub.D.sup.20 = 1.5664                          26     F CHF.sub.2                                                                          ##STR165##     M.p.: 54-56° C.                           27     F CHF.sub.2                                                                          ##STR166##     n.sub.D.sup.20 = 1.4715                          28     F CHF.sub.2                                                                          ##STR167##     n.sub.D.sup.20 = 1.4799                          29     Cl                                                                              CF.sub.3                                                                           ##STR168##     n.sub.D.sup.20 = 1.4741                          30     Cl                                                                              CF.sub.3                                                                           ##STR169##     M.p.: 60° C.                              31     F CF.sub.3                                                                           ##STR170##     M.p.: 54° C.                              32     F CF.sub.3                                                                           ##STR171##     n.sub.D.sup.20 =  1.5953                         __________________________________________________________________________

PREPARATION OF THE STARTING COMPOUNDS EXAMPLE II-1 ##STR172##

A mixture of 750 ml of phosphorus oxychloride, 157.2 g (1.2 mols) of5-methyl-2,4-thiazolidinedione and 4 ml of dimethylformamide is heatedunder reflux, with stirring, until gas evolution has virtually ceased(about 6 hours). The reaction mixture, when it has cooled, issubsequently poured out, a little at a time, onto 5 kg of ice, with goodstirring. It is then extracted by shaking three times with about 1 literof methylene chloride at a time, the methylene chloride is distilled offin vacuo and the residue (187.3 g) is distilled. At 86° C./18 mbar,159.1 g (78.9% of theory) of 2,4-dichloro-5-methylthiazole (in a purityof 99.9%, determined by gas chromatography), of boiling point 203° C.(at atmospheric pressure), are obtained.

EXAMPLE II-2 ##STR173##

205 g (1.22 mols) of 2,4-dichloro-5-methylthiazole are chlorinated in achlorination apparatus (compare DE-OS (German Published Specification)2,844,270, pages 18 and 23), at the boil (temperature in the reactionvessel initially 205° C.), under UV irradiation from an Hg high pressurelamp. As soon as the temperature in the reactor has reached 235° C., thechlorination is stopped. Conversion about 80%. According to analysis bygas chromatography, the chlorination mixture has the followingcomposition:

19.5% of 2,4-dichloro-5-methylthiazole

79.0% of 5-chloromethyl-2,4-dichlorothiazole

1.5% of 2,4-dichloro-5-(dichloromethyl)-thiazole.

Fractional distillation using a packed column of 30 cm effective length,packed with glass rings of 2 mm diameter and 2 mm length, gives, at aboiling point of 118°-119° C./20 mbar, 145 g (72% of theory, based onconversion) of 5-chloromethyl-2,4-dichlorothiazole, having a refractiveindex n_(D) ²⁰ =1.5835; purity, according to gas chromatography: 98.5%.

EXAMPLE II-3 ##STR174##

100 g (1.41 mols) of chlorine are passed into a mixture of 59 g (0.35mol) of 2,4-dichloro-5-methylthiazole and 450 ml of tetrachloromethanein the course of 6 hours at the reflux temperature (about 80° C.).According to analysis by gas chromatography, the reaction mixtureconsists of:

2.0% of 5-chloromethyl-2,4-dichlorothiazole

89.4% of 2,4-dichloro-5-(dichloromethyl)-thiazole

7.9% of 2,4-dichloro-5-(trichloromethyl)-thiazole

Fractional distillation using a packed column of about 30 cm lengthgives, as the main runnings at boiling point 122°-125° C./20 mbar, 48.5g of 2,4-dichloro-5-(dichloromethyl)-thiazole, in a purity, determinedby gas chromatography, of 94.0%. Yield (based on 100% pure product):54.8% of theory.

EXAMPLE II-4 ##STR175##

340 g of chlorine are passed into 1,008 g (6 mols) of2,4-dichloro-5-methylthiazole dissolved in 600 ml of tetrachloromethaneover the course of 6 hours at 200°-210° C., and thereafter a further 860g of chlorine (making a total of 1,200 g=16.9 mols) are passed in overthe course of 7 hours at between 210° and 240° C. The gas chromatogramof the crude mixture shows that of the four possible2,4-dichlorothiazoles (5-methyl-, 5-chloromethyl-, 5-dichloromethyl- and5-trichloromethyl-), only 2,4-dichloro-5-(trichloromethyl)-thiazole ispresent. Working up by distillation gives, at 136°-137° C./19 mbar, 773g (49.1% of theory, based on the amount of chlorine employed) of2,4-dichloro-5-(trichloromethyl)-thiazole. Purity according to gaschromatography: 97.1%.

EXAMPLE II-5 ##STR176##

430 g (1.8 mols) of 2,4-dichloro-5-dichloromethyl-1,3-thiazole arefluorinated with 650 ml of anhydrous hydrogen fluoride in a stainlesssteel autoclave at 137°-140° C./18-22 bar. The hydrogen chloride formedis released continuously. After completion of the reaction, the excesshydrogen fluoride is stripped off in vacuo at room temperature, theresidue is poured onto ice water and taken up in methylene chloride, andthe methylene chloride solution is dried over sodium sulphate anddistilled. 275 g (74.3% of theory) of2,4-dichloro-5-difluoromethyl-1,3-thiazole are obtained, boiling pointat 12 mbar/65°-66° C.; n²⁰ =1.5070, together with 30 g of more highlyfluorinated constituents.

EXAMPLES II-6 AND II-7 ##STR177##

230 g (1.12 mols) of 2,4-dichloro-5-difluoromethyl-1,3-thiazole arestirred with 131 g (2.25 mols) of potassium fluoride in 339 ml oftetramethylenesulphone for 3 hours at 160° C. The fluorinated product isthen distilled off in vacuo until the boiling point of thetetramethylene sulphone is reached.

Redistillation gives:

76 g (40% of theory) of 2,4-difluoro-5-difluoromethyl-1,3-thiazole ofboiling point 108°-9° C.; refractive index n_(D) ²⁰ =1.4108 and

47 g (22.4% of theory) of2-fluoro-4-chloro-5-difluoromethyl-1,3-thiazole of boiling point 141°-3°C.; refractive index n_(D) ²⁰ =1.4528, as well as

40 g of starting compound.

EXAMPLES II-8 AND II-9 ##STR178##

227 g (0.836 mol) of 2,4-dichloro-5-trichloromethyl-1,3-thiazole arefluorinated with 200 ml of anhydrous hydrogen fluoride in a stainlesssteel autoclave at 50° C./3-8 bar. The hydrogen chloride formed isreleased continuously. After completion of the reaction (about 4 hours),the mixture is cooled to room temperature and the excess hydrogenfluoride is stripped off in vacuo down to 100 mbar. The residue ispoured onto ice water and taken up in methylene chloride, and themethylene chloride solution is dried over sodium sulphate and distilled.

84 g (39.5% of theory) of2,4-dichloro-5-difluorochloromethyl-1,3-thiazole of boiling point 76°-8°C./18 mbar; refractive index n_(D) ²⁰ =1.5120, and

67 g (33.7% of theory) of2,4-dichloro-5-dichlorofluoromethyl-1,3-thiazole of boiling point105°-107° C./18 mbar; refractive index n_(D) ²⁰ =1.5539 as well as

12 g of starting compound, are obtained.

If the reaction is carried out at 60° C./5 bar,2,4-dichloro-5-difluorochloromethyl-1,3-thiazole is obtained in a yieldof 71% of theory.

EXAMPLE II-10 ##STR179##

500 g (1.84 mols) of 2,4-dichloro-5-trichloromethyl-1,3-thiazole arefluorinated with 740 ml of anhydrous hydrogen fluoride in a stainlesssteel autoclave at 120°-140° C./25-30 bar for 3 hours. The hydrogenchloride formed is released continuously. After completion of thereaction, the mixture is cooled and the excess hydrogen fluoride isstripped off in a water pump vacuum down to 100 mbar. The residue ispoured onto ice water and taken up in methylene chloride, and themethylene chloride solution is dried over sodium sulphate and distilled.

280 g (68.5% of theory) of 2,4-dichloro-5-trifluoromethyl-1,3-thiazoleof boiling point 50° C./16 mbar; refractive index n_(D) ²⁰ =1.4710, and

63 g of partially fluorinated compounds, are obtained.

USE EXAMPLES

In the use example which follows, the compound shown below was employedas the comparison substance: ##STR180##2-(4,5-dichloro-1,3-thiazol-2-yloxy)-N,N-diethyl-acetamide (known fromEP-OS (European Published Specification) 18,497).

EXAMPLE A Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. After 3weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

Distinct superiority in herbicidal activity, with comparable crop plantselectivity, relative to the state of the art are shown in this test by,for instance, the compounds according to the following preparationexamples: 12, 14, 15, 16, 17, 24 and 25.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A 4,5-disubstituted 1,3-thiazol-2-yloxyacetamideof the formula ##STR181## in which R¹ is fluorine or chlorine,R² isalkyl with 1 to 4 carbon atoms or halogenomethyl, and R³ and R⁴ eachindependently is alkyl with 1 to 8 carbon atoms, alkenyl or alkinyl eachwith 2 to 8 carbon atoms, cycloalkyl or cycloalkenyl each with 3 to 7carbon atoms being unsubstituted or substituted by alkyl with 1 to 4carbon atoms, alkoxy, alkoxyalkyleneoxy or alkoxyalkyl each with 1 to 8carbon atoms in the individual alkyl or alkylene moieties, halogenoalkylwith 1 to 8 carbon atoms and 1 to 5 halogen atoms, aralkyl with 6 to 10carbon atoms in the aryl moiety and 1 to 2 carbon atoms in the alkylmoiety, or aryl with 6 to 10 carbon atoms and optionally substituted byat least one of halogen, alkyl, alkoxy or alkylthio each with 1 to 4carbon atoms, and halogenoalkyl, halogenoalkoxy or halogenoalkylthioeach with 1 to 2 carbon atoms and 1 to 5 halogen atoms, or nitro or R³and R⁴ together with the nitrogen atom to which they are bonded form a5- to 7-membered heterocyclic ring optionally substituted by alkyl with1 to 6 carbon atoms optionally in the form of a fused ring system, arylwith 6 to 10 carbon atoms optionally in the form of a fused ring system,or dioxyalkylene with 2 to 3 carbon atoms,with the exception of thecompound 2-(4-chloro-5-difluoromethylthiazol-2-yloxy)-acetic acidN-methyl-anilide.
 2. A compound according to claim 1, in whichR² ismethyl, trifluoromethyl, difluoromethyl, fluoromethyl, trichloromethyl,dichloromethyl, chloromethyl, fluorodichloromethyl ordifluorochloromethyl, and R³ and R⁴ each independently is alkyl with 1to 6 carbon atoms, alkenyl or alkinyl each with 2 to 6 carbon atoms,cycloalkyl or cycloalkenyl with 5 to 7 carbon atoms which is optionallymono- to tri-substituted by methyl and/or ethyl, alkoxy,alkoxyalkyleneoxy or alkoxyalkyl each of which has 1 to 6 carbon atomsin the individual alkyl moieties, halogenoalkyl with 1 to 6 carbon atomsand 1 to 5 halogen atoms, benzyl as well as phenyl which optionally hasone to three substituents independently selected from the groupconsisting of methyl, ethyl, methoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, fluorine, chlorine or nitro; orR³ and R⁴ together with the nitrogen atom to which they are bonded froma heterocyclic ring of the formula ##STR182## which optionally has oneto three substituents independently selected from the group consistingof methyl, ethyl and phenyl.
 3. A compound according to claim 2, whereinsuch compound is 2-(4-fluoro-5-difluoromethylthiazol-2-yloxy)-aceticacid N-methyl-anilide of the formula ##STR183##
 4. A compound accordingto claim 2, wherein such compound is2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)-acetic acidN-methyl-anilide of the formula ##STR184##
 5. A compound according toclaim 2, wherein such compound is2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)-acetic acidN,N-hexamethylenimide of the formula ##STR185##
 6. A compound accordingto claim 2, wherein such compound is2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)-acetic acidN,N-diethylamide of the formula ##STR186##
 7. A compound according toclaim 2, wherein such compound is2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)-acetic acid N-methoxy,N-(but-2-yl)-amide of the formula ##STR187##
 8. A compound according toclaim 2, wherein such compound is2-(4-chloro-5-trifluoromethyl-thiazol-2-yloxy)-acetic acid N-isopropyl,N-(2-ethoxyethoxy)-amide of the formula ##STR188##
 9. The compositionaccording to claim 10, wherein such compoundis2-(4-fluoro-5-difluoromethylthiazol-2-yloxy)acetic acid N-methylanilide, 2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)acetic acidN-methyl anilide, 2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)aceticacid N,N-hexamethylenimide,2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)acetic acid N,N-diethylamide, 2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)acetic acidN-methoxy, N-(but-2-yl)-amide or2-(4-chloro-5-trifluoromethylthiazol-2-yloxy)acetic acid N-isopropyl,N-(2-ethoxyethoxy)-amide.
 10. A herbicidal composition comprising acarrier and a herbicidally effective amount of a 4,5-disubstituted1,3-thiazol-2-yloxyacetamide of the formula ##STR189## in which R¹ isfluorine or chlorine,R² is alkyl with 1 to 4 carbon atoms orhalogenomethyl, and R³ and R⁴ each independently is alkyl with 1 to 8carbon atoms, alkenyl or alkinyl each with 2 to 8 carbon atoms,cycloalkyl or cycloalkenyl each with 3 to 7 carbon atoms beingunsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy,alkoxyalkyleneoxy or alkoxyalkyl each with 1 to 8 carbon atoms in theindividual alkyl or alkylene moieties, halogenoalkyl with 1 to 8 carbonatoms and 1 to 5 halogen atoms, aralkyl with 6 to 10 carbon atoms in thearyl moiety and 1 to 2 carbon atoms in the alkyl moiety, or aryl with 6to 10 carbon atoms and optionally substituted by at least one ofhalogen, alkyl, alkoxy or alkylthio each with 1 to 4 carbon atoms, andhalogenoalkyl, halogenoalkoxy or halogenoalkylthio each with 1 to 2carbon atoms and 1 to 5 halogen atoms, or nitro or R³ and R⁴ togetherwith the nitrogen atom to which they are bonded form a 5- to 7-memberedheterocyclic ring optionally substituted by alkyl with 1 to 6 carbonatoms optionally in the form of a fused ring system, aryl with 6 to 10carbon atoms optionally in the form of a fused ring system.
 11. A methodof combating unwanted vegetation which comprises applying to suchvegetation or to a locus from which it is desired to eliminate suchvegetation a herbicidally effective amount of a1,3-thiazol-2-yloxyacetamide of the formula ##STR190## in which R¹ isfluorine or chlorine,R² is alkyl with 1 to 4 carbon atoms orhalogenomethyl, and R³ and R⁴ each independently is alkyl with 1 to 8carbon atoms, alkenyl or alkinyl each with 2 to 8 carbon atoms,cycloalkyl or cycloalkenyl each with 3 to 7 carbon atoms beingunsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy,alkoxyalkyleneoxy or alkoxyalkyl each with 1 to 8 carbon atoms in theindividual alkyl.
 12. The composition according to claim 10, wherein thecompound is 2-(4-chloro-5-difluoromethylthiazol-2-yloxy))acetic acidN-methylanilide of the formula ##STR191##
 13. The method according toclaim 11, wherein the compound is2-(4-chloro-5-difluoromethylthiazol-2-yloxy)acetic acid N-methylanilideof the formula ##STR192##